O-phenyl-n-alkoxy-(thiono)-phosphoric(phosphonic) acid ester amides

ABSTRACT

O - PHENYL-N-ALKOXY-(THIONO)-PHOSPHORIC(PHOSPHONIC) ACID ESTER AMIDES OF THE FORMULA:   R-O-NH-P(=X)(-R&#39;&#39;)-O-R&#34;   IN WHICH   R IS ALKYL WITH 1 TO 6 CARBON ATOMS, R&#39;&#39; IS ALKYL OR ALKOXY WITH 1 TO 6 CARBON ATOMS, R&#34; IS PHENYL OPTIONALLY SUBSTITUTED BY AT LEAST ONE OF HALOGEN, NITRO, CYANO, LOWER ALKYL, ALKOXY, CARBALKOXY AND ALKYLMERCAPTO WITH 1 TO 6 CARBON ATOMS, AND X IS OXYGEN OR SULFUR,   WHICH POSSESS INSECTICIDAL, ACARICIDAL, NEMATOCIDAL, FUNGICIDAL AND BACTERICIDAL PROPERTIES.

United States Patent 3,773,861 O-PHENYL-N-ALKOXY-(THIONOyPHOSPHORIC (PHOSPHONIC) ACID ESTER AMIDES Wolfgang Hofer, Wuppertal-Elberfeld, Ingeborg Hammann, Cologne, Bernhard Homeyer, Opladen, and Wilhelm Stendel, Wuppertal-Elberfeld, Germany, assignors to Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Filed Aug. 17, 1972, Ser. No. 281,361 Claims priority, application Germany, Sept. 1, 1971, P 21 43 756.9 Int. Cl. A0111 9/36'; C07f 9/24 US. Cl. 260-949 7 Claims ABSTRACT OF THE DISCLOSURE O phenyl-N-alkoxy-(thiono)-phosphoric(phosphonic) acid ester amides of the formula:

which possess insecticidal, acaricidal, nematocidal, fungicidal and bactericidal properties.

The present invention relates to and has for its objects the provision of particular new O-phenyl-N-alkoxy- (thiono)-phosphoric(phosphonic) acid ester amides, i.e., O-alkyl-O-phenyl-N-alkoxy-phosphoric acid ester amides, O-phenyl-N-alkoxy-alkanephosphonic acid ester amides and their thiono analogues, which possess insecticidal, acaricidal, nematocidal, fungicidal and bactericidal properties, active compositions in the form of mixtures of such compounds with solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new way especially for combating pests, e.g. insects, acarids, nematodes, fungi and bacteria, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

It is known from German published specification DAS 1,142,605 that O-phenyl-N,N-dialkyl-thiono-phosphonic acid ester amides, such as 0-(3-methyl-4-methyl-mercapto- (Compound A) or 2-chloro-4-tert.-butyl-(Compound B) or 2,4 dichlorophenyl)-N,N-dimethyl-thionoethanephosphonic acid ester amide (Compound C), possess insecticidal properties. Furthermore, 0,0-diphenyl-N-methoxyphosphoric acid ester amide (Compound D) has already been described in the literature by Cates, J. Med. Chem., vol. 11 (1968), No. 2, pages 382-383.

The present invention provides O-phenyl-N-alkoxy- (thiono)-phosphoric(phosphonic) acid ester amides of the formula:

RONH

in which R is alkyl with 1 to 6 carbon atoms,

R is alkyl or alkoxy with 1 to 6 carbon atoms,

R" is phenyl optionally substituted by at least one of halogen, nitro, cyano, lower alkyl, alkoxy, carbalkoxy and alkylmercapto with 1 to 6 carbon atoms, and

X is oxygen or sulfur.

Preferably, in the 'Formula I, R is straight-chain or branched lower alkyl with 1 to 3 carbon atoms, R' is straight-chain or branched lower alkyl or al-koxy with 1 to 4 carbon atoms, and R" is phenyl which is optionally substituted one or more times by chlorine, cyano, methoxy, ethoxy, methylmercapto, ethylmercapto, straight or branched lower alkyl with 1 to 4 carbon atoms and carbo-lower alkoxy with 1 to 4 carbon atoms in the alkoxy moiety.

Surprisingly, the O-phenyl-N-alkoxy-(thiono)-phosphoric(phosphonic) acid ester amides according to the invention are distinguished, in comparison to previously known compounds of analogous structure, by higher insecticidal, especially soil-insecticidal, and acaricidal activity in addition to nematocidal, fungicidal and bactericidal action. Furthermore, the substances according to the invention have proved of value in combating ectoparasites in the veterinary field. They thus represent a genuine enrichment of the art.

The invention also provides a process for the production of an O-phenyl-N-alkoxy-(thiono)-phosphoric(phosphonic) acid ester amide of the Formula I in which an O-alkylhydroxylammonium chloride of the general formula:

RONH .HCl (H) X, R and R: have the above-mentioned meanings, and Hal is halogen, preferably chlorine,

in the presence of an acid-binding agent, or (b) a (thiono)-phosphoric(phosphonic) acid ester dihalide or acid dihalide of the general formula X Hal (TV) 4 Hal in which R, X and Hal have the above-mentioned meanings, in the presence of an acid-binding agent and, without isolation of the intermediate product, the reaction mixture is subsequently treated with a phenol of the formula HOR" (V) in which R" has the above-mentioned meanings, in the presence of further acid-binding agent.

If O-n-propyl-hydroxylamine hydrochloride and O-nbutyl O-(4-ethylmercapt0-3-methyl-phenyl)-thionophosphoric acid ester chloride or 0-n-propyl-hydroxylammonium chloride, O-n-butylphosphoric acid ester dichloride and 2,4-dichlorophenol are used as the starting ma- 3 4 terials, the courses of the reaction can be represented by pose. These include, above all, aliphatic and aromatic opthe following formula schemes: tionally chlorinated hydrocarbons such as benzene, tolu- OH: on.

7104Hn S 2moles of 1|C H9O S I H G acid acceptor [I Q flCiH1-0NH2-HCl P-o s 01H; P-O 3 0,11.

-2HC1 Cl nC;H 0NH (IIa) (IIIa) (46) (VI) (b) amino 0 2moles 11041100 0 ll acid acceptor nc,n1-0NH-no1 P-c1 1 -01 CIQOH -HCl Cl nC H ONH (118) (Va) 1 (IVa) Cl flCaHoO O +acid acceptor \I! Q -----------i P-O Cl nC;H ONH 47) (VIII The O-alkylhydroxylammonium chlorides (II), 0- ene, xylene, benzine, methylene chloride, chloroform, carphenyl-(thiono)-phosphoric(phosphonic) acid ester habon tetrachloride and chlorobenzene, ethers such as dilides (III), (thiono)-phosphoric(phosphonic) acid ester ethyl ether, dibutyl ether and dioxane, ketones such as dihalides or acid dihalides (IV) and phenols (V) required acetone, methyl ethyl ketone, methyl isopropyl ketone and as starting substances have already been described in the methyl isobutyl ketone, and nitriles such as acetonitrile literature and can be prepared in accordance with known and propionitrile.

processes, even on an industrial scale. All customary acid-binding agents can be used as acid As examples of O-alkylhydroxylammonium chlorides acceptors. Alkali metal carbonates and alcoholates, such (II) there may be mentioned: 0-methy1-, O-ethyl-, O-nas sodium and potassium carbonate, methylate or ethylpropyland O-iso-propyl-hydroxyammonium chloride. ate, and also aliphatic, aromatic or heterocyclic amines,

Examples of O-phenyl (thiono) phosphoric(phosfor example triethylamine, dimethylaniline, dimethylphonic) acid ester halides (III) and (thion0)-phosphoric benzylamine and pyridine, and also alkali metal hy- (phosphonic) acid ester dihalides or acid dihalides (IV) droxides, have proved particularly suitable.

include: O-methyl-, O-ethyl-, O-n-propyl-, O-iso-propyl-, The reaction temperatures can be varied over a wide O-n-butyl-, O-iso-butyl-, O-sec.-butyland O-tert.-butyl-O- range. In general, the reaction is carried out at about 0 phenylor -O-(4-cyanophenyl)-, -O-(2,4,5-trichlorophento 100, preferably about 0 to 45 C.

yl)-, -O-(3-methyl-phenyl)-, -O-(3-ethylphenyl)-, -O-(3- The reaction is generally carried out under normal propylphenyl)-, -O-(3-tert.-butyl-phenyl)-, -O-(2,6-dipressure.

chlorophenyl)-, -O-(4 chlorophenyl)-, -O-(2 carbome- When carrying out the process variant (a), an approxthoxyphenyl)-, -0-( 2 carbethoxyphenyl)-, -O (2 carboimately 10% excess of the hydroxylammonium compopropoxyphenyl)-, -O-(2 carbobutoxyphenyl)-, -O-(3- nent (II) is in most cases reacted with the phosphoric methyl 4- methylmercaptophenyl)-, -O-(3-ethyl-4-ethylacid compound (III) in the presence of approximatelyl mercaptophenyl)-, -O-(2,4 dimethylmercapto-S-methylmolar equivalents of acid acceptor, for example at 30 to phenyl)-, -O-(3-methoxyphenyl)-, -O-(3-ethoxyphenyl)-, 40 C. using one of the indicated solvents. After stirring -O-(2-chloro-4-methy1phenyl)-, -O-(2-chloro-4-ethylphenfor several hours at elevated temperatures, the mixture yl)-, -O-(2-chloro-4-tert.-butylphenyl)-phosph0ric acid may be Worked up in the usual manner.

ester chloride and their thiono analogues as well as the In the Process Variant the hydfoxylammonhlm corresponding O-(4-cyanophenyl)-, O-(4-chlorophenyl)-, derivative (III), preferably in approximately 10% excess, O-(2,4,5-trichlorophenyl)-, 0-(3-methylpheny1)-, O-( 3- and 2 molar equivalents of acid acceptor are added dropethylphenyl)-, O-(3-propylphenyl)-, O- (Z-carbomethoxywise to the acid dihalide (IV), for example at 0 to 5 C., phenyl)-, O-(Z-carboethoxyphenyl)-, O (2 carboisoand the mixture is then treated with the phenol compopropoxyphenyl)-, 0-(2-carbobutoxyphenyl)-, O-(3- hnent (V), and a further molar equivalent of acid acceptor yl-4-methy]mercaptophenyl)-, O-(2,4dimethylmercapto- (relative to the acid dihalide) at room temperature, with phenyl)-, 0-(2,4-dimethylmercapto-5-methylphenyl)-, O- stirring. The reaction mixture may be stirred for several (2-h1oro-4 meth 1 h n 1)-, -O-(2-ch1QfQ-4-ethylpheny1)- hours at room temperature and may then be worked up methane-, -ethane-, -n-propane-, -iso-propane-, -n-butane-, in the 1181181 manner.

-i b t ..sec,-butane-, and -tert.-butane-phospho i The substances according to the invention are in most acid ester chloride and their thiono analogues, and also cases Obtained in the form of colorless to slightly colored methane-, ethane-, n-propane-, iso-propane-, n-butane-, oils which cannot be distilled without decomposition but iso-butane, sec.-butane and tert.-butanephosphonic acid can be freed 0f the last Volatile Constituents, and can in dihalide and the corresponding thiono analogues, and also t y he P y eo-called g distillation," that O-methyl-, O-ethyl-, O-n-propyl-, O-iso-propyl, O-n- 1s to say prolonged heating under reduced pressure at butyl-, O-iso-butyl-, O-ge -butyld t t, b 1 h moderately elevated temperatures. The substances are phoric acid ester dichloride and the corresponding thiono especially characterized y the refractive index- Some Of analogues, them, however, are obtained in a crystalline form with a As examples of phenol derivatives (V) there may be Sharp characteristic melting Point.

mentioned: 2-, 3- and 4-Ch101'0-, 2,4- and 2,6-dichloro-, As already mentioned, the new -p y 2,4,5 and 2,4,6-trichloro-, pentachloro-, 2-, 3- and 4- )r p dp p acid ester amides are 5- 1 1. 4 1 .5- 1 distinguished by an outstanding insecticidal, especially h 2 1- 4- 2 3- 3 4- and 2 h 1 soil-insecticidal, and acaricidal activity towards plant, 3,5-dimethyl, 4-chloro-, 2-tert.-butyl-, 2-iso-propyl-, 3- hygiene and Storage pests and ectoparasitesy possess ethy1-5-methyl-, 2- and 3-methoxy-, 2-eth0Xy-, 3-methyl-4- a d action against sucking and against biting insects methylmercapto-, 3,5-dimethyl-4-methylmercapto-, 2-carand mites At the Same time y display 310W bomethoxy-, 2-carboethoxyand Z-carbisopropoxyphenol. p y xi i y a d lso display some nematocidal, fungi- The reaction of both process variants is preferably cidal and bactericidal properties.

carried out in the presence of a solvent or diluent. Prac- For these reasons, the compounds according to the ticaly all inert organic solvents can be used for this purinvention may be successfully used as pesticides in plant protection and the protection of stored products, as well as in the hygiene and veterinary field.

To the sucking insects contemplated herein there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicate), the bean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi), the pea. aphid (Macrosz'phum pisi) and the potato aphid (Macrosiphum solanifolii), the currant gall aphid (Cryptomyzus korschelti), the rosy apple aphid (Sappaphis mali), the mealy plum aphid (Hyalopterus amndim's) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspidiotus hederae) and the soft scale (Lecam'wm hesperidum) as well as the grape mealybug (Pseudacoccus maritimus); thrips (Thysanoptera), such as Hercinothrz'ps femoralz's, and bugs, for example the beet bug (Piesma quadrata), the red cotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), the assassin bug (Rhodnius prolixus) and Chagas bug (Triatoma infestans) and, further, cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus; and the like.

In the case of the biting insects contemplated herein, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella macaulipennis), the gypsy moth (Lymantria dispar), the browntail moth (Euproctis ohrysorrhoea) and tent caterpillar (Malacosomas neustria); further, the cabbage moth (Mamestra brassicae) and the cutworm (Agrostis segetum), the large white butterfly (Pieris brassicate), the small winter moth (Chez'matobia brumata), the green oak trotrix moth (Tortrix viridana), the fall armyworm (Laphygma frugiperda) and cotton worm (Prodenia litura), the ermine moth (Hyponomcuta padella), the Mediterranean flour moth (Ephestia kt'thniella) and greater wax moth (Galleria mellonella); and the like.

Also to be classed with the biting insects contemplated herein are beetles (Coleoptera), for example the granary weevel (Sitophilus granarius=Calandra granaria), the Colorado beetle (Leptinotarsa decemlineata), the dock beetle (Gastrophysa vin'dula), the mustard beetle (Phae don cochleariae), the blossom beetle (Meligethes aeneus), the raspberry beetle (Byturus tomentosus), the bean weevil (Bruehidius=Acanthoscelides obtectus), the leather beetle (Dermestes frischi), the khapra beetle (Trogoderma granurium), the flour beetle (Tribolium castaneum), the northern corn billbug (Calandra or Sitaphilus zeamais), the drugstore beetle (Stegobiwm paniceumi), the yellow mealworm (Tenebrio molitor) and the saw-toothed grain beetle (Oryzaephilus surinamensis), and also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockch-afer (Mela- .lontha melolontha); cockroaches, such as the German cockroach (Blattella garmanica), American cockroach (Periplm eta ameripana), Madeira cockroach (Leucophaea or Rhyparobia muderae), oriental cockroach (Blatta orienralis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscuu) as well as Henschoutedenia flexivitta; further, Orthoptera, for example the house cricket (Aclieta domestic-us); termites such as the eastern subterranean termite (Reticulitermes fllavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such as the vinegar fly '(Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Musca domestica), the little house fly (Fannia canicularis), the black blow fly (Phormia regina) and bluebottle fly (Calliphora erythrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi); and the like.

With the mites (Acari) contemplated herein there are classed, in particular, the spider mites (Tetranychidae) such as the two-spotted spider mite (Tetranychus telarius: Tetranychus althaeae or Tetranychus urticae) and the European red mite (Paratetranychus pil0sus=Pan0nychus ulmi), gall mites, for example the black currant gall mite (Eriophyes ribis) and tarsonemids, for example the broad mite (Hemitarsonemus latus) and the cyclamen mite (Tarsonemus palladius); finally, ticks, such as the relapsing fever tick (Ornithodorus moubata); and the like.

When applied against hygiene pests and pests of stored products, particularly flies and mosquitoes, the compounds of the invention are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with conventional inert (i.e. plant compatible or herbicidally inert) pesticide diluents or extenders, i.e. diluents, carriers or extenders of the type usable in conventional pesticide formulations or compositions, e.g. conventional pesticide dispersible carrier vehicles such as gases, solutions, emulsions, suspensions, emulsifiable concentrates, spray powders, pastes, soluble powders, dusting agents, granules etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticide dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticide surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: aerosol propellants which are gaseous at normal temperatures and pressures, such as Freon; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), cycloalkanes (e.g. cyclohexane, etc.), paraffins (e.g. petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, glycol, etc.) as well as ethers and esters thereof (e.g. glycol monomethyl ether, etc.), amines (e.g. ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, clays, alumina, silica, chalk, i.e. calcium carbonate, talc, attapulgite, montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g. highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.); whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-active agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/ or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/ or liquid dispersible carrier vehicles and/ or with other known compatible active agents, especially plant protection agents, such as other insecticides, acaricides,

nematocides, fungicides and bactericides, or rodenticides, herbicides fertilizers, growth-regulating agents, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 01-95% by weight, and preferably 0.5-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.000l%, preferably 0.01-1%, by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprises mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/ or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as anemulsifying agent and/or a dispersing agent, and an amount of the active compound which is eflfective for the purpose in question and which is generally between about 0.0001-95%, and preferably 0.01-95 by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very efi'ective atomizing equipment, in finely divided form, e.g. average particle diameter of from 50- 100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about to 1000 g./hectare, preferably 40 to 600 g./hectare, are sufficient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about to about 95% by weight of the active compound or even the 100% active substance alone, e.g. about 20-100% by weight of the active compound.

Furthermore, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. insects, acarids, fungi, bacteria and nematodes, and more particularly methods of combating at least one of insects and acarids, which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, (e) such nematodes, ((1) such fungi, (e) such bacteria, and (f) the correspondingly habitat thereof, i.e., the locus to be protected, a correspondingly combative or toxic amount, i.e., an insecticidally, acaricidally, nematocidally, fungicidally or bactericidally effective amount, of the particular active compound of the invention alone or together with a carrier vehicle as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The synthesis, unexpected superiority and outstanding activity of the particular new compounds of the present invention are illustrated, without limitation, by the following examples:

EXAMPLE 1 Myzus test (contact action) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl-polyglycol-ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphids (Myzus persicae) are sprayed with the preparation of the active compound until dripping wet.

After the specified periods of time, the degree of destruction is determined as a percentage: 100% means that all the aphids are killed whereas 0% means that none of the aphids are killed.

The active compounds, the concentrations of the active compounds, the evaluation times and the results can be seen from the following Table 1:

TABLE 1 (Myzus test) Active Degree of compound destruction concentrain percent tion in after 1 Active compounds percent day (I? (D) 0. 1 0 OHaO-NH-P (O-Q) (known) CH; (A) 0.1 40 0215\5 0.01 0

/P-- O- S CHI zhN (known) 18 CzHsO S 0. 1 100 ii 0.01 /PO- Cl GHaO-NH 35 0211\5Sl 0.1 100 l -o-o1 0.01 100 CH\ONH TABLE 1--Conttnued Active com- Degree or pound condestruction centrati'on inpercent Activecompounds tnpercent sitar-Nays 45 CH: 0.1 100 CflHlO O 0.01 100 P-() -SCH| CHaO-NE 24 CH: 0.1 100 02H: 8 0.01 100 \ll 7 I 0.001 06 /PO SCH: CH|O-NH 22 oo-oomom). 0.1 100 CHr\S 0.01 70 CHaO-NH 11 C:H|0\S a! 12% CHIONE CaHrO\B| 00b} 18:

Canto-NH 7 EXAMPLE 2 Tetranychus test (resistant) j, Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl-poly-glycol-ether To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate so obtained is diluted with water to the desired concentration.

Bean plants (Phaseolus vulgaris), which have a height of approximately 10-30 cm., are sprayed with the preparation of the active compound until dripping wet. These TABLE 2 (Tetrsnychus test) (resistant) Active com- Degree 0! pound eon destruction centration in percent Active compounds in percent after 2 days (D) 0.1 o -0Q) (known) CH: (A) 0. 1 30 0%: SI 0.01 0

-O SCH: (CHOlN CIH:O\S

'i -o- CHaO-N b l 17... & Ci 0.1 00

CEO-N l Active compounds in percent after 2 days CHsON i -oc1 C2H50-N{ l c,n,o s o 95 -o more). CHsO-N cmo s 0 -O SCH! OHIO-NE 01H, s 0.1 so

I \ILOQCI cnioazf 1 on, 0.1 98 CIHBO\% 0.01 so P-O son: CH:O-N

on .1 as c=m0 o o fl-O SCH: cmo-Nfi a CZHIS CH: 0.1 90

\II a P-O -cm CHlON en,

2 C2Hs 8 CH: 0.1 98

EXAMPLE 3 Critical concentration test/soil insects Test insect: Phorbia brassicae Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl-polyglycol-ether The concentration of the active compound in the preparation is of practically no importance; only the amount of active compound per unit volume of soil, which is given in p.p.m., is decisive. The soil is filled into pots, lettuce is sown in and the pots are kept at a greenhouse temperature of 27 C. After 4 weeks, the lettuce roots are examined for infestation with nematodes, and the degree of eflFectiveness of the active compound is determined as a percentage. The degree of eifectiveness is 100% when infestation is completely avoided; it is 0% when the infestation is exactly the same as in the case of the control plants in untreated soil which has been infested in the test nematodes. same manner.

TABLE 3 (Phorbia braalicae/grubs in soil) fier, and the concentrate thus obtained is diluted with water to the desired concentration.

Degree of destruction in percent at an active compound concentration of- 20 10 5 2.5. Active compounds p.p.m. p.p.m. p.p.m. p.p.m

C:HsO\fi /PO SCH: CHz-NH 3o c1 100 100 so GIHEO s P-O- Cl CHtO-NH 35 CzH\afi 100 100 90 50 CHzO-NH a4 or 100 100 5c 13-0 0] CHaO-NH P0 Cl CHIO-N 2L CH: 100 100 so P-O- CH: CHzO-NE C:HsO\fi /P--O- Ci CHlO--NH CzHsO S (E) 50 0 P-N-SCCh (known) EXAMPLE 4 About 20 fly larvae (Lucilia cuprina) are introduced Test with parasitary fly larvae into a test tube which contains about 2 cm. of horse Solvent: 35 parts by weight of ethylene-polyglycol-monomethyl-ether Emulsifier: 35 parts by weight of nonylphenol-polyglycolether In order to produce an appropriate preparation of active compound, 30 parts by weight of the active substance in question are mixed with the indicated amount of solvent which contains the abovementioned proportion of emulsimuscle. 0.5 ml. of the active compound preparation are applied to this horseflesh. After 24 hours, the degree of destruction inpercent is determined. Herein, 100% denotes that all larvae have been killed and 0% denotes that no larvae have been killed.

The active compounds examined, the concentrations TABLE 4 (Test with parasitary fly larvae) Degree 01 Active destruction compound inpercent concentration (Lucilia Active compounds in p.p.m. cuprma) NH- OCH; SCH;

Degree of Active destruction compound lnpercent concentration (I/uciZia Active compounds in p.p.m. cuprina) S C1 is l88 H 30 50 CIHuO-T-O Cl 10 NH--O CH:

35- S 300 100 I! 30 100 C:HsI"0 Cl 3 100 NH-OCH:

27 s 300 100 II 100 100 CzHs-P-O 30 50 1o 0 NH-O cm 26 CH8 300 100 s 100 100 ll 30 100 CH O1"0 SCH; 10 o NHOCHs Cl 300 100 s 100 100 ll mo (hHr-P-OQ-Cl 10 100 i NET-OCH:

24 CH; 300 100 i 3g 10g CgHs-li-O SCHS NH-OCHa 33- C1 300 100 s 100 100 II so 100 CzH 0P0-Cl 10 100 1 3 0 NH-O OH:

45. O CH; Sgg u 3 o C2Hs01.-0 H-a NH--O CH3 EXAMPLE 5 phosphoric acid diester chloride in 70 ml. of acetonitrile was subsequently added dropwise to the reaction mixture 7 CH 5 at 30 to 40 C., the mixture was stirred for a further 4 can) 3 3 hours at 40 C., the solid constituents were filtered ofl, {L S CHa the solvent was removed under reduced pressure and the CH (1) residue was taken up in 100 ml. of benzene. After wash- 3 ing with water and drying the benzene phase over' sodi 60 g. (0.44 mole) of potassium carbonate were suspended in 150 ml. of acetonitrile. 19 g. (0.22 mole) of 0-methylhydroxylammonium chloride were added to this suspension, a solution of 59 g. (0.2 mole) of O- um sulfate, the solvent was again stripped off under reduced pressure and the residue was subjected to incipient distillation at 0.1 mm. Hg and 80 C. 50 g. (82% of theory) of O-ethyl-O-(3-methyl-4-methylmercaptoethyl-O-(B-methyl 4 methylmercaptophenyl)-thjon0- phenyl)-N-methoxy-thionophosphoric acid ester amide TABLE-Continued Physical properties (refractive Yield index, melt- (percent of Compound ing point) theory) 31 OCH F 70 C. 77

CL'HIO s p /P-O GHaO-NH 32 CaH5O\fi m)=1.5350 40 CHzO-N CzHsO S \H P-O Cl CHaO-NH 34 Cl 1m"=1.6542 52 CHIO S \ll P-O- Cl CHaON 35 C2H\rfi nD =L5663 79 oH30-N{ 36 Cl 1m=1.5579 66 C2Ha0\fi P--O Cl CHaO-NH 37 CH1 Fp. Iii-56 C. 72

C2H50\fi PO SC CH O-NH CHI EXAMPLE 6 4 were then added dropwise. Thereafter 33 g. (0.3 mole) of C1 triethylamine were added dropwise to the reaction mix- CZHbO 0 l ture of 25 C. The mixture was stirred for a further 4 hours at 25 C. The salt-like precipitate which formed P 0 e1 was filtered off and the filtrate was washed with Water. CHSCPNH (38) After drying the organic phase over sodium sulfate, the solvent was stripped off under reduced pressure and the 27 g. (0.33 mole) of O'-methylhydroxylammonium chloride and '67 g. (0.66 mole) of triethylamine were dissolved in 500 ml. of chloroform and this solution was added dropwise, at 0 to 5 C., to a solution of 49 g. (0.3 mole) of O-ethylphosphoric acid ester dichloride in 500 ml. of chloroform. Thereafter the mixture was stirred for a further 30 minutes at to C. and 42 g. (0.26 mole) of 3,4-dichlorophenol in 100 ml. of chloroform residue was subjected to incipient distillation at 0.1 mm.

1 Hg and 70 C. 58 g. (74% of theory) of O-ethyl-O-(3,4-

Physical ropertles refractive Yield index melting (percent of Compound point) theory) 39 Cl nn =1.4950 50 CzHsO 0 \ll /PO C (CH3) CHaO-NH 40 C2HaO\(") flD =1.50 0 68 CHaO-NH 41 CzHuO O nn =1A902 68 ll /PO CHsO-NH 42 OH; Fp. 70-73 C.

/PO S CH: GH|ONH l S OH:

CHaO-NH Other compounds which can be similarly produced include:

butyl O (3 nitro 4 isopropoxyphenyl) N- butoxythionophosphoric acid ester amide,

O (4 isopropylmercaptophenyl) N methoxybutanephosphonic acid ester amide,

and the like.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What we claim is:

1. An 0 phenyl-N-alkoXy-(thiono)-phosphoric(phosphonic) acid ester amide of the formula:

in which R is alkyl with 1 to 6 carbon atoms,

R is alkyl or alkoxy with 1 to 6 carbon atoms,

R" is phenyl substituted by at least one of halogen, nitro,

lower alkyl, cyano, alkoxy, carbalkoxy and alkylmercapto with 1 to 6 carbon atoms, and

X is oxygen or sulfur.

2. A compound according to claim 1 in which R is lower alkyl, R is lower alkyl or alkoxy, and R" is phenyl optionally substituted by at least one of chlorine, cyano, methoxy, ethoxy, methylmercapto, ethylmercapto, lower alkyl and carbo-lower alkoxy.

3. The compound according to claim 1 wherein such compound is O-ethyl-O-(3-methyl-4-methylmercaptophenyl)-N-methoxy-thionophosphonic acid diester amide of the formula:

CzHgO S Zi O S OH I CHao-NH 4. The compound according to claim 1 wherein such compound is O-(2,4-dichlorophenyl)-N-methoxy-ethanethionophosphonic acid ester amide of the formula:

TABLE contlnued Physical properties (refractive Yield index, melt- (percent of Compound mg point) theory) 43 C 0- 0 031171 nn =1A928 37 C2H5O\(H) /P 0 CHaO-NH 44. C2H5O\fi np=1.4916 57 CHaO-NH 45 CHa flD =L5312 71 P- O S OH:

CHsO-NH 5. The compound according to claim 1 wherein such compound is O-ethyl-(3,4-dichlorophenyl)-N-methoxythionophosphoric acid diester amide of the formula:

CHaO-NH 6. The compound according to claim 1 wherein such compound is O (4 chlorophenyl)-N-methoxy-ethanethionophosphonic acid ester amide of the formula:

Caro-NH i -O-Qs om CHaONH References Cited UNITED STATES PATENTS 3,711,582 1/1973 Schrader et al. 260959 LEWIS GO'ITS, Primary Examiner R. L. RAYMOND, Assistant Examiner U .8. Cl. X.R.

UNITED STATES PATENT 0mm tw J:

(IIZI QFIIPI(IILUPI ()1? 1()I111I(31TI()PQ fanenh Nd. 3,773,861 V d. November 20,;l973 Invencor() Wolfgang Hoffif at E1 Page l of 2 It is certified that error appears in the aboyg-identified patent and that said Letters Pafient arg hazeby corrected as shown belouz' ,,[Col. 4, 11q-46, hange"(III)"O I1 E Col, 5, 1ifi:5; cprfect spelling 0f "pfsicae";

H ling 25; coriet spelling 9f "ficulipenfiis"; 1ine"28; rrt sp11ing of "Agrotig"; I line 29, rfect spel1ing of "Brssicae";

"tortrix" (fiirsfi ccurrence).

1ine-31, q rregt gpllingof Co}. 9, Camp? 34; Tble 1, under Dgr of dstruqtion in percent s. after 1 da9 change 9108 to LOO -Q. I

Gompduh-36,-Tb1e 1, under heading UDegrge of destrutiofi in percent after l day? change "90" to 99 .q,

- .Compound 14, Table 1, correct formula to rgad as follows:

' i 1 4 I v I C1H S I ma v v Cl a Col. l3,.conpound'39, Table 2, in'the chemical formula, change I I. S I a -1.-

H u P- f Column Compgund 36,-Tab1e.1 under the heading "Degree of Destruction in percent ffer 1 day", "1G9" $hou1d read loo-Q1.

Col. 3,"1ine 28, hnge "hydroxyammoniumfi to hydtokylammbnium -y e e .2 0. I v I z ID-O-- e 01 mm 7 v 3.

I Signed. and sealed this 19th day of November 1974.

T2273? 1 UNiTED STATES PA'LENTQFFICE V I CERTIFICATE OF CORRECTION Patent No. 3,773,861 Dated Inventor) I Page 2 of 2 It 18 certified that; error appears in the ab'oye-identified patent and that said Letters Patent are heteby corrected as shown below:

C01. 16',.'Tab1 e 4, I Cjompound lychange I B IYl to 10333 -v-, (:01; 16 Ta b 1e Cpflipi updsj,COIfI'GCC fOrmUIB ,to readas follews: r s i Z Q Q B I I scHj NH-OCH3 C01. .26, elaim cbrrect the formule to feed as follows:

read as fbllods (SEAL) Attest:

' McC OY M. GIBS ON JR.

Attesting Officer CQMAR'sHA'LL DANN Comissiqner of Patents- 

